Continuous one-step synthesis of N-doped titania under supercritical and subcritical water conditions for photocatalytic reaction under visible light

N-doped titania was prepared continuously by one-step synthetic method under supercritical and subcritical water conditions using titanium(IV)tetraisopropoxide (TTIP) and nitric acid as a titania precursor and nitrogen source, respectively. The synthesized N-doped titania particles were characterized by XRD, N₂-adsorption, TEM, XPS, UV-vis diffuse reflectance spectroscopy. N-doped titania was successfully synthesized and its crystalline structure was homogenous anatase phase with high surface area. The absorption edge of synthesized N-doped titania shifted into the visible light region compared with commercial titania P25. All synthesized N-doped titania have higher photocatalytic activity than P25 under visible light irradiation. The photocatalytic activity of N-doped titania synthesized under supercritical water condition was the highest for the degradation of methyl orange under visible light due to the larger crystallite size compared with the N-doped titania synthesized under subcritical water condition.     

Pd2+ reduction and gasochromic properties of colloidal tungsten oxide nanoparticles synthesized by pulsed laser ablation

Tungsten oxide nanoparticles were fabricated by a pulsed laser ablation method in deionized water using the first harmonic of a Nd:YAG laser (λ=1064 nm) at three different laser pulse energies (E1 =160, E2 =370 and E3 =500 mJ/pulse), respectively. The aim is to investigate the effect of laser pulse energy on the size distribution and gasochromic property of colloidal nanoparticles. The products were characterized by dynamic light scattering (DLS), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and UV-Vis spectroscopy. The results indicated that WO₃ nanoparticles were formed. After ablation, a 0.2 g/l PdCl₂ solution was added to activate the solution against hydrogen gas. In this process Pd²⁺ ions were reduced to deposit fine metallic Pd particles on the surface of tungsten oxide nanoparticles. The gasochromic response was measured by H₂ and O₂ gases bubbling into the produced colloidal Pd–WO₃. The results indicate that the number of unreduced ions (Pd²⁺) decreases with increasing laser pulse energy; therefore, for colloidal nanoparticles synthesized at the highest laser pulse energy approximately all Pd²⁺ ions have been reduced. Hence, the gasochromic response for this sample is nearly reversible in all cycles, whereas those due to other samples are not reversible in the first cycle.     

Triblock copolymer-templated synthesis of porous TiO2 and its photocatalytic activity

Mixed amorphous and anatase-type titania particles were synthesized using non-ionic triblock copolymer as surfactant template and TiOSO₄ as inorganic precursor through sol–gel process. The as-prepared materials were characterized by X-ray diffraction spectroscopy, scanning and transmission electron microscopy, specific surface area, Fourier-transformed infrared spectroscopy, and diffuse reflectance ultraviolet–visible spectroscopy. The template material could be easily removed by extracting with dichloromethane and was confirmed by infrared spectroscopy. X-ray diffraction pattern reveals the crystalline part of as-prepared product as a framework of anatase phase. From the N₂ adsorption–desorption analysis, the as-prepared sample has a surface area of 301 m²/g with pore size distribution narrowly centered around 6 nm. The photodegradation of indigo carmine including kinetics, effect of pH, and recyclability of the product were investigated. The photocatalytic results showed that the as-synthesized titania could efficiently degrade indigo carmine under ultraviolet irradiation and showed higher photocatalytic activity than the commercial Degussa P25–TiO₂.     

Characteristics of γ-Al2O3 nanoparticles generated by continuous-wave laser ablation in liquid

Laser ablation in liquid is one of the most widely investigated methods for generating various nanoparticles (NPs) that are difficult to produce using other means. In this paper, we report the generation of Al-oxide NPs by continuous-wave (CW) fibre laser ablation of corundum (α-Al₂O₃) target submerged in deionised water. The effects of CW fibre laser power and radiation time have been investigated. Characterisation of the NPs generated, in terms of size, size distribution, shape, chemical composition, and phase structure, was carried out by means of high-resolution transmission electron microscopy (HR-TEM), high angle annular dark field (HAADF) in scanning-transmission (STEM) mode, energy-dispersive X-ray spectroscopy (EDS), and X-ray diffraction (XRD). The results show that the average size of Al-oxide NPs, in the range of 17 to 29 nm, increased with increasing the laser power and laser exposure time, and the NPs are dominated by stoichiometric γ-Al₂O₃ with a minor phase of α-Al₂O₃. The mechanism involved in the CWLAL is also discussed.     

Generation and characterization of NiO nanoparticles by continuous wave fiber laser ablation in liquid

Pulsed laser ablation in liquid (PLAL) has been widely applied for the generation of nanoparticles (NPs). We report on the generation of NiO NPs using a high-power, high-brightness continuous wave (CW) fiber laser source at a wavelength of 1,070 nm. Characterization of such NPs in terms of size distribution, shape, chemical composition, and phase structure was carried out by transmission electron microscopy (TEM), high-resolution TEM equipped with energy-dispersive X-ray (EDX), and X-ray diffraction (XRD). The results revealed the formation of NiO NPs in water with an average size of 12.6 nm. The addition of anionic surfactant sodium dodecyl sulfate (SDS) reduced the size of NiO NPs down to 10.4 nm. The shape of the NPs was also affected by the SDS, showing the change of shapes from spherical domination in water to tetragonal with increased SDS concentrations. Furthermore, the NiO NPs generated in water and SDS solutions were dual phase containing both cubic and rhombohedral structures. It was also found that the NiO NPs were single crystalline in nature irrespective of the size and shape.     

Mössbauer and MCD spectroscopy of the Fe3S4 nanoparticles synthesized by the thermal decomposition method with two different surfactants

Greigite (Fe₃S₄) nanoparticles (NPs) were fabricated by the thermal decomposition method using two different surfactants: oleylamine (OLA) and 1-hexadecylamine (HDA). In both cases, the synthesized NPs were characterized as the Fe₃S₄ nanocrystals with minor inclusions of Fe₉S₁₁ phase. FT-IR spectroscopy and thermo-gravimetric analysis allow concluding about OLA or HDA shells covering magnetic core of NPs. Mössbauer spectra has revealed deviations of iron ions distribution among crystal positions from that presented in literature for pure greigite. In accordance with these deviations, the pronounce changes are observed in the magnetic circular dichroism (MCD) spectra which manifest themselves as the spectrum shift to higher energies of electromagnetic waves and redistribution of the MCD maximum intensities. These effects are associated with a change in the density of electronic states in the samples due to the redistribution of iron ions between octahedral and tetrahedral positions in nanocrystals under the influence of surfactants.     

Synthesis of composite gold/tin-oxide nanoparticles by nano-soldering

Composite Au–SnO₂ nanoparticles (NPs) are synthesized by nano-soldering of pure Au and SnO₂ NPs. The multi-step process involves synthesis of pure Au and SnO₂ NPs separately by nanosecond pulse laser ablation of pure gold and pure tin targets in deionized water and post-ablation laser heating of mixed solution of Au colloidal and SnO₂ colloidal to form nanocomposite. Transmission Electron Microscopy (TEM) and High-Resolution Transmission Electron Microscopy (HRTEM) were used to study the effect of laser irradiation time on morphology of the composite Au–SnO₂ NPs. The spherical particles of 4 nm mean size were obtained for 5 min of post-laser heating. Increased mean size and elongated particles were observed on further laser heating. UV–vis spectra of Au–SnO₂ nanocomposites show red shift in the plasmon resonance absorption peak and line shape broadening with respect to pure Au NPs. The negative binding energy shift of Au 4f_7/2 peak observed in X-ray Photoelectron Spectra (XPS) indicates charge transfer in the nano-soldered Au–SnO₂ between gold and tin oxide and formation of soldered nanocomposite.     

Nucleation and growth of silver nanoshells through copper vapor laser irradiation

Silica core–silver shell, silver nanoshells (NSs), have been synthesized by an innovative laser-based approach. The NSs’ nucleation and growth progressed upon the pulse strikes of a copper vapor laser on a colloidal solution containing silver and silica nanoparticles (NPs). The silver NPs were separately synthesized by ablation of a silver target in deionized water by a 1064 nm Q-switched Nd:YAG laser. The dependence of silver NSs’ growth on the laser exposure time has been systematically studied by UV–VIS absorption spectroscopy technique. Transmission electron microscopy was exploited as well to visually confirm the NSs’ evolution through the process.     

Observation of carbon‐facilitated phase transformation of titanium dioxide forming mixed‐phase titania by confocal Raman microscopy

Confocal Raman microscopy, a relatively new and advanced technique, is found to be suitable for imaging the chemical morphology below the submicrometer scale. It has been employed to probe the phase transformation of carbon‐containing titania (TiO₂) nanopowder and titania thin film subjected to laser annealing. The observation of phase transformation from the anatase phase to the rutile phase at high laser power annealing is attributed to carbon inclusion inside or on the surface of titania. Upon annealing, carbon could react with the oxygen of titania and create oxygen vacancies favoring the transformation from the anatase to the rutile phase. This study provides evidence for the carbon‐assisted phase transformation for creating carbon‐containing mixed‐phase titanium dioxide by laser annealing. We explicitly focus on the presence of carbon in the phase transformation of TiO₂ using confocal Raman microscopy. In all of the investigated samples, mixed anatase/rutile phases with carbon specifically was found at the rutile site. X‐ray diffraction (XRD), scanning electron microscopy (SEM) and energy‐dispersive spectroscopy (EDS) studies have been performed in addition to Raman mapping to verify the mixed‐phase titania formation. Copyright © 2010 John Wiley & Sons, Ltd.     

Synthesis and characterization of platinum nano sized particles by laser ablation in C<Subscript>2</Subscript>H<Subscript>6</Subscript>O<Subscript>2</Subscript> solution

Platinum nano sized particles (Pt NPs) are superior catalysts for many intentions, such as glucose sensors, cancer therapy, gas sensors, etc. Here, Pt NPs were produced by pulsed laser ablation in C₂H₆O₂ solution using Q-switched Nd:YAG laser, for the first time. Then, the influence of the laser fluence during synthesis of them was investigated; and they were characterized by UV–vis spectroscopy, TEM, FE-SEM, XRD, FT-IR, and Raman spectroscopy. The results showed that with increasing laser fluence, the mean particle size of the spherical NPs enhanced. Meanwhile, they had a polycrystalline cubic structure. Correspondingly, the plasmon peak position of generated NPs in the absorption spectra shifted from 257 to 266 nm, with a rise of laser fluence. The IR and Raman spectroscopy was used to achieve the information about the surface state of Pt NPs. We propose that the optimum adjusted laser fluence is an important factor to increase the ablation efficiency.     

Nanosized titania encapsulated silica particles using an aqueous TiCl4 solution

In this study, sub-micron sized silica particles were encapsulated with nanosized titania particles using an aqueous TiCl₄ solution. The particle size distribution of the synthesized titania particles in the coating layer was estimated to be 10 nm from X-ray powder diffraction and transmission electron microscopy. The thickness of the coating layer ranged from a few nm to about 30 nm from transmission electron microscopy analysis. Zeta potential analysis demonstrated the presence of a titania particle coating layer and the extent of its coverage on the surface of silica particles. X-ray photoelectron spectroscopy analysis also demonstrated that titania particles were successfully deposited on the surface of core silica particles from the chemical shift of binding energies of O 1s, Ti 2p and Si 2p.     

Nano- and microdot array formation by laser-induced dot transfer

Fabrication of FeSi₂ nano- and microdot array was performed by utilizing droplet ejection through laser-induced forward transfer, which we named laser-induced dot transfer (LIDT). An amorphous FeSi₂ alloy source film on a transparent support was illuminated from the support by a nanosecond excimer laser pulse patterned into migcrogrid form, resulting in size- and site-controlled dot deposition. Micro-Raman spectroscopy confirmed β-FeSi₂ semiconducting crystalline phase even on unheated substrates. Moreover, the microdots exhibited near-infrared photoluminescence at the peak wavelength of 1.57 μm, which comes from the β-FeSi₂ crystalline phase precipitated during the LIDT process. The dot size was successfully reduced to approximately 500 and 300 nm in diameter and height, respectively. This technique is useful for integrating functional nano- and microdots under atmospheric room-temperature conditions.     

The application of Raman and anti-stokes Raman spectroscopy for in situ monitoring of structural changes in laser irradiated titanium dioxide materials

The use of Raman and anti-stokes Raman spectroscopy to investigate the effect of exposure to high power laser radiation on the crystalline phases of TiO₂ has been investigated. Measurement of the changes, over several time integrals, in the Raman and anti-stokes Raman of TiO₂ spectra with exposure to laser radiation is reported. Raman and anti-stokes Raman provide detail on both the structure and the kinetic process of changes in crystalline phases in the titania material. The effect of laser exposure resulted in the generation of increasing amounts of the rutile crystalline phase from the anatase crystalline phase during exposure. The Raman spectra displayed bands at 144 cm⁻¹ (A1g), 197 cm⁻¹ (Eg), 398 cm⁻¹ (B1g), 515 cm⁻¹ (A1g), and 640 cm⁻¹ (Eg) assigned to anatase which were replaced by bands at 143 cm⁻¹ (B1g), 235 cm⁻¹ (2 phonon process), 448 cm⁻¹ (Eg) and 612 cm⁻¹ (A1g) which were assigned to rutile. This indicated that laser irradiation of TiO₂ changes the crystalline phase from anatase to rutile. Raman and anti-stokes Raman are highly sensitive to the crystalline forms of TiO₂ and allow characterisation of the effect of laser irradiation upon TiO₂. This technique would also be applicable as an in situ method for monitoring changes during the laser irradiation process.     

Microstructural study of thin films of 5 mol% gadolinia doped ceria prepared by pulsed laser ablation

Microstructural characterization of thin films of 5 mol% gadolinia doped ceria films deposited by pulsed laser ablation in the energy range 100–600 mJ/pulse has been investigated, as deposited films were found to be nanocrystalline with preferred orientation. X-ray diffraction analysis revealed that the size of the nanocrystals of doped ceria does not vary significantly with increasing laser energy, whereas transmission electron microscopy study showed a uniform distribution of nanocrystal of 8–10 nm for energies ≤200 mJ/pulse and nanocrystals embedded in a large crystalline matrix of doped ceria for energies in the range 400–600 mJ/pulse. Although the laser-ablated films were totally free from secondary phases, lattice imaging of the large grained doped ceria showed growth-induced defects, such as dislocations and ledges.     

Hydrodynamic cavitation: A feasible approach to intensify the emulsion cross-linking process for chitosan nanoparticle synthesis

Chitosan nanoparticles (NPs) exhibit great potential in drug-controlled release systems. A controlled hydrodynamic cavitation (HC) technique was developed to intensify the emulsion crosslinking process for the synthesis of chitosan NPs. Experiments were performed using a circular venturi and under varying operating conditions, i.e., types of oil, addition mode of glutaraldehyde (Glu) solution, inlet pressure (P_in), and rheological properties of chitosan solution. Palm oil was more appropriate for use as the oil phase for the HC-intensified process than the other oil types. The addition mode of water-in-oil (W/O) emulsion containing Glu (with Span 80) was more favorable than the other modes for obtaining a narrow distribution of chitosan NPs. The minimum size of NPs with polydispersity index of 0.342 was 286.5 nm, and the maximum production yield (P_y) could reach 47.26%. A positive correlation was found between the size of NPs and the droplet size of W/O emulsion containing chitosan at increasing P_in. Particle size, size distribution, and the formation of NPs were greatly dependent on the rheological properties of the chitosan solution. Fourier transform infrared spectroscopy (FTIR) analysis indicated that the molecular structure of palm oil was unaffected by HC-induced effects. Compared with ultrasonic horn, stirring-based, and conventional drop-by-drop processes, the application of HC to intensify the emulsion crosslinking process allowed the preparation of a finer and a narrower distribution of chitosan NPs in a more energy-efficient manner. The novel route developed in this work is a viable option for chitosan NP synthesis.     

Effects of the ZnSe concentration on the structural and optical properties of ZnSe/PVA nanocomposite thin film

This study investigated the effects of ZnSe nanoparticles (NPs) on the structural and (linear and nonlinear) optical properties of polyvinyl alcohol (PVA) thin film. Three samples of ZnSe NP-doped PVA thin films with different concentrations of ZnSe were produced on a glass substrate. The ZnSe NPs were synthesized by pulsed laser ablation of the ZnSe bulk target immersed in distilled water using a 1064 nm wavelength and a high frequency pulsed Nd:YAG laser. The optical bandgap energies of the films were extracted from their UV-Vis-NIR absorption spectra. The corresponding energy bandgaps of the nanocomposite films declined as the ZnSe NPs doping concentration increased. X-ray diffraction analysis was used to characterize the crystalline phases of the ZnSe/PVA nanocomposite films. The concentration-dependent nonlinear optical absorption and nonlinear refraction behaviors of the films after exposure to 532-nm nanosecond laser pulses were investigated using the Z-scan technique. The nonlinear absorption response of the films was positive when measured using an open aperture scheme, which was attributed to the two-photon absorption mechanism. In addition, the nonlinear refraction indices had a negative value and they increased as the concentration of ZnSe NPs in the films increased.     

Spectroscopic analysis of the riboflavin—serum albumins interaction on silver nanoparticles

Metallic nanoparticles (NPs) supported on oxides thin films are commonly used as model catalysts for studies of heterogeneous catalysis. Several 4d and 5d metal NPs (for example, Pd, Pt and Au) grown on alumina, ceria and titania have shown strong metal support interaction (SMSI), for instance the encapsulation of the NPs by the oxide. The SMSI plays an important role in catalysis and is very dependent on the support oxide used. The present work investigates the growth mechanism and atomic structure of Rh NPs supported on epitaxial magnetite Fe₃O₄(111) ultrathin films prepared on Pd(111) using the Molecular Beam Epitaxy (MBE) technique. The iron oxide and the Rh NPs were characterized using X-ray photoelectron spectroscopy (XPS), low-energy electron diffraction and photoelectron diffraction (PED). The combined XPS and PED results indicate that Rh NPs are metallic, cover approximately 20 % of the iron oxide surface and show height distribution ranging 3–5 ML (monolayers) with essentially a bulk fcc structure.     

Nano-ionic thin films of gadolinia-doped ceria prepared by pulsed laser ablation

Microstructural properties of nano-ionic thin films of gadolinia-doped ceria (GDC) prepared by pulsed laser ablation from sintered targets of gadolinia (5–20 mol%) doped ceria are investigated. The ionic conductivity measurements of the sintered pellets showed a decrease in the activation energy from 1.1 to 0.65 eV for 5 and 30 mol% gadolinia-doped ceria, respectively. The microstructural properties of the GDC films as a function of substrate temperature, oxygen partial pressure, and laser energy show that the films are polycrystalline in the entire range of substrate temperature. The grain size is found to increase with increasing temperature up to 873 K. Further improved crystallinity is noticed for the films grown with oxygen partial pressure of 0.1–0.2 mbar. X-ray diffraction and transmission electron microscopy (TEM) reveal nanocrystalline grains with textured growth along <111> orientation in these films at low substrate temperature and at lower oxygen partial pressure. TEM study shows a uniform distribution of nanocrystal of 8–10 nm for energies ≤200 mJ/pulse, and nanocrystals embedded in a large crystalline matrix of doped ceria for energies in the range 400–600 mJ/pulse. Raman spectroscopy also confirms the defects in these films. The study also reveals that the substrate temperature and oxygen partial pressure could influence preferred orientation, while the laser energy could significantly influence defect concentration in these films. Invited paper presented at the Third International Conference on Ionic Devices (ICID 2006), Chennai, Tamilnadu, India, Dec. 7–9, 2006.     

Pulsed laser induced synthesis of scheelite-type colloidal nanoparticles in liquid and the size distribution by nanoparticle tracking analysis

Pulsed laser ablation (PLA) of ceramic target in liquid phase was successfully employed to prepare calcium tungstate (CaWO₄) and calcium molybdate (CaMoO₄) colloidal nanoparticles. The crystalline phase, particle morphology and optical property of the colloidal nanoparticles were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and Raman spectroscopy. The produced stable colloidal suspensions consisted of the well-dispersed nanoparticles showing a spherical shape. The mechanism for the laser ablation and nanoparticle forming was discussed under consideration of photo-ablation process. Nanoparticle tracking analysis using optical microscope combined with image analysis was proposed to determine the size distribution function of the prepared colloidal nanoparticles. The mean size of the CaWO₄ and CaMoO₄ colloidal nanoparticles were 16 and 29 nm, with a standard deviations of 2.1 and 5.2 nm, respectively.     

Characterization of Ag and Au nanoparticles created by nanosecond pulsed laser ablation in double distilled water

Pulsed laser ablation of Ag and Au targets, immersed in double-distilled water is used to synthesize metallic nanoparticles (NPs). The targets are irradiated for 20 min by laser pulses at different wavelengths—the fundamental and the second harmonic (SHG) (λ = 1064 and 532 nm, respectively) of a Nd:YAG laser system. The ablation process is performed at a repetition rate of 10 Hz and with pulse duration of 15 ns. Two boundary values of the laser fluence for each wavelength under the experimental conditions chosen were used—it varied from several J/cm² to tens of J/cm². Only as-prepared samples were measured not later than two hours after fabrication. The NPs shape and size distribution were evaluated from transmission electron microscopy (TEM) images. The suspensions obtained were investigated by optical transmission spectroscopy in the near UV and in the visible region in order to get information about these parameters. Spherical shape of the NPs at the low laser fluence and appearance of aggregation and building of nanowires at the SHG and high laser fluence was seen. Dependence of the mean particle size at the SHG on the laser fluence was established. Comments on the results obtained have been also presented.